Processing and Stable Oils

Processing and Stable Oils

G. R. ListG. R. List

Food and Industrial Oil

Research Unit

National Center for

Agricultural Utilization Research

USDA/ARS, Peoria, IL

Food and Industrial Oil

Research Unit

National Center for

Agricultural Utilization Research

USDA/ARS, Peoria, IL

Presented at the American Heart Association Trans Fat Conference,

Washington D.C., October 10–11, 2006

Presented at the American Heart Association Trans Fat Conference,

Washington D.C., October 10–11, 2006

1894–96Hydrogenated clear frying

9–11110–112Salad oil

3280–82Shortening base

4065–68Margarine / spread base

% TransIodine ValueOil

1894–96Hydrogenated clear frying

9–11110–112Salad oil

3280–82Shortening base

4065–68Margarine / spread base

% TransIodine ValueOil

22Stick margarine oil45Dairy creamer fat

13Tub margarine oil43Donut frying shortening

25Industrial margarine32Icing shortening

13Cocoa butter replacer32All-purpose shortening

35Cracker spray oil43Cube frying shortening

% TransProduct

% TransProduct

Food Service Products

22Stick margarine oil45Dairy creamer fat

13Tub margarine oil43Donut frying shortening

25Industrial margarine32Icing shortening

13Cocoa butter replacer32All-purpose shortening

35Cracker spray oil43Cube frying shortening

% TransProduct

% TransProduct

Food Service Products

Trans Fatty Acid Contents of Hydrogenated Soybean OilsTrans Fatty Acid Contents of Hydrogenated Soybean Oils

879Coconut

1,617Edible Tallow

522Palm Kernel

538Olive

631 Soybean, canola, corn, cottonseed account for 97.4%

Palm

Other

10021.99521,995

0.40.08888Safflower

1.10.245245Sunflower

1.10.250250Peanut

7.31.5981,598Canola

3.80.834834Cottonseed

7.71.6831,683Corn

78.617.317,300Soybean

%Billion PoundsMillion PoundsOil

879Coconut

1,617Edible Tallow

522Palm Kernel

538Olive

631 Soybean, canola, corn, cottonseed account for 97.4%

Palm

Other

10021.99521,995

0.40.08888Safflower

1.10.245245Sunflower

1.10.250250Peanut

7.31.5981,598Canola

3.80.834834Cottonseed

7.71.6831,683Corn

78.617.317,300Soybean

%Billion PoundsMillion PoundsOil

U.S. Usage of Edible Vegetable Oils2004–2005

U.S. Usage of Edible Vegetable Oils2004–2005

* Projected

725.8753243102006*

210.658941622005

351.71111572802004

266.6521191832003

371.82061663822002

333.82511493872001

Million PoundsExportUse

Production1000 Metric tons

Year Ending

Production / Domestic Use of Sunflower Oil

Production / Domestic Use of Sunflower Oil

* Projected

725.8753243102006*

210.658941622005

351.71111572802004

266.6521191832003

371.82061663822002

333.82511493872001

Million PoundsExportUse

Production1000 Metric tons

Year Ending

Trans-Free SolutionsTrans-Free Solutions

InteresterificationLiquid oils / stearines: soy, cottonseed, palm

ChemicalEnzymatic

Fractionation of Tropical FatsPalm

Palm Kernel

Modified Hydrogenation ProcessesPressure-controlled

ElectrochemicalSupercritical Fluids

Noble Metal CatalystsModified Catalysts

InteresterificationLiquid oils / stearines: soy, cottonseed, palm

ChemicalEnzymatic

Fractionation of Tropical FatsPalm

Palm Kernel

Modified Hydrogenation ProcessesPressure-controlled

ElectrochemicalSupercritical Fluids

Noble Metal CatalystsModified Catalysts

Blending Liquid Soft Oils with Harder Components

Animal Fats / Edible Tallows

Modified Composition OilsLow Linolenic: soy, canola

High Oleic: soy, corn, sunflowerHigh Saturate: soy

Naturally Stable OilsLow in Linolenic Acid

CornCottonseed

High-oleic / mid-oleic sunflower

Blending Liquid Soft Oils with Harder Components

Animal Fats / Edible Tallows

Modified Composition OilsLow Linolenic: soy, canola

High Oleic: soy, corn, sunflowerHigh Saturate: soy

Naturally Stable OilsLow in Linolenic Acid

CornCottonseed

High-oleic / mid-oleic sunflower

Combinations of Interesterification, Hydrogenation, FractionationCombinations of Interesterification, Hydrogenation, Fractionation

Continuous processBatch process

No post-processingRequires post-processing—killing

of catalysts, washing out soaps,

bleaching to remove color bodies

No side productsReaction prone to side products—

soaps, methyl esters,

mono/diglycerides formed

Catalyst / enzyme expensiveCatalyst (sodium methoxide)

sensitive to moisture

Feedstock sensitive to moisture,

free fatty acids

Solid fat curves are steeper, sharply

melting—better functionality

Solid fat index / solid fat curves

are relatively flat

Reaction is specific (1,3 positions)Reaction not specific—triglycerides

conform to random distribution

Continuous processBatch process

No post-processingRequires post-processing—killing

of catalysts, washing out soaps,

bleaching to remove color bodies

No side productsReaction prone to side products—

soaps, methyl esters,

mono/diglycerides formed

Catalyst / enzyme expensiveCatalyst (sodium methoxide)

sensitive to moisture

Feedstock sensitive to moisture,

free fatty acids

Solid fat curves are steeper, sharply

melting—better functionality

Solid fat index / solid fat curves

are relatively flat

Reaction is specific (1,3 positions)Reaction not specific—triglycerides

conform to random distribution

InteresterificationChemical Enzymatic

InteresterificationChemical Enzymatic

Interesterification ProcessInteresterification Process� Salad oils have low

amounts of TFA's� Low IV hydrogenated fats

have low amounts of TFA's

� Salad oils have low amounts of TFA's

� Low IV hydrogenated fats have low amounts of TFA's

� The interesterification process will produce a desi rable slope to the SFI/SFC curve of the finished product

� The interesterification process will produce a desi rable slope to the SFI/SFC curve of the finished product

BlendTankBlendTank

Fully Hydro Veg Oil

Fully Hydro Veg Oil

Liquid Oil

Liquid Oil

InteresterificationInteresterification

Baking Fat

or

MargarineBase

Baking Fat

or

MargarineBase

Liquid Oil

Liquid Oil

HardStockHardStock

Enzymatic InteresterificationEnzymatic Interesterification

Oil Mill Gazeteer, June 2004Oil Mill Gazeteer, June 2004

Product Tank

Product Tank

Feed TankFeed Tank

Small Reactor SeriesSmall Reactor Series

* Lipozyme ® / Novozyme

80–1001600400

40–50800200

20–25400100

Capacity T / Day

Kg Total

Enzyme

Kg Enzyme*/ Reactor

* Lipozyme ® / Novozyme

80–1001600400

40–50800200

20–25400100

Capacity T / Day

Kg Total

Enzyme

Kg Enzyme*/ Reactor

De Smet Enzymatic InteresterificationDe Smet Enzymatic Interesterification

Oil Mill Gazeteer, June 2004Oil Mill Gazeteer, June 2004

Solid Fat Index and Drop Melting Points of Enzymatically Interesterified Soy Oil / Soy Stearine Blends

Solid Fat Index and Drop Melting Points of Enzymatically Interesterified Soy Oil / Soy Stearine Blends

Drop Melting PointsDrop Melting PointsSolid Fat IndexSolid Fat Index

5050 6060 7070 8080 9090 100100 11011000

1010

2020

3030

4040

5050

6060

55

1515

2525

3535

4545

5555

Sol

id F

at In

dex

(%)

Sol

id F

at In

dex

(%)

Temperature (ºF)Temperature (ºF)1010 2020 3030 4040 5050 6060

8080

9090

100100

110110

120120

130130

140140

Dro

p P

oint

(ºF

)D

rop

Poi

nt (

ºF)

% Titer% Titer

Dry Multiple Fractionation of Palm OilDry Multiple Fractionation of Palm Oil

Palm Oil

I.V. 51I.V. 51––5353

Super Stearin

I.V. 17I.V. 17––2121

Soft Stearin

I.V. 40I.V. 40––4242

Hard Stearin

I.V. 32I.V. 32––3636

Olein

I.V. 57I.V. 57––5959

"Oleins"

Soft PMF

I.V. 42I.V. 42––4848

Super Olein

I.V. 64I.V. 64––6666

Hard PMF

I.V. 32I.V. 32––3636

Top Olein

I.V. 70I.V. 70––7272

1st Stage1st Stage 2nd Stage2nd Stage 3rd Stage3rd Stage

recycling

Solid Fat Content of Palm Oil Fractions by NMR

Solid Fat Content of Palm Oil Fractions by NMR

Olein

Olein

Palm O

il

Palm O

il Soft P

MF

Soft P

MF

Soft Stearin

Soft Stearin

Hard Stearin

Hard Stearin

0000 55 1010 1515 2020 2525 3030

Temperature ºCTemperature ºC3535 4040 4545 5050 5555 6060

1010

2020

3030

4040

5050

6060

7070

8080

9090

100100

SF

C (

%)

SF

C (

%)

Hard P

MF

Hard P

MF

Super S

tearin

Super S

tearin

E. Deffense Lipid Technology

(1995)

E. Deffense Lipid Technology

(1995)

J. Hasman "Trans Suppression in Hydrogenated Oils," Inform 6 1206 (1995)

� Low temperatures, high pressures, high catalyst con centration produce about 50% less trans than normal

� High pressures and catalyst concentration are deter rents to commercial use� Work about 10 years ahead of its time

King, et. al. "Hydrogenation of Soybean Oil in Mixtures of Super C ritical Carbon Dioxide and Hydrogen," JAOCS, 78 107–113 (2001)

List, et. al. "Hydrogenation of Soybean Oil: Effect of Pressure o n Selectivity,"JAOCS 77 311–314 (2000)

� Trans suppression up to 80% — slow reaction rates at low t emperatures and high pressures (i.e. 120ºC, 250–500 lbs.)

� Studies strongly suggest that a window exists where pressure and temperature can be used to make a selective reaction rather tha n non-selective

Warner, et. al. "Electrochemical Hydrogenation of Soybean Oil," JAOCS 77 (2000)

� Shows promise in laboratory studies

J. Hasman "Trans Suppression in Hydrogenated Oils," Inform 6 1206 (1995)

� Low temperatures, high pressures, high catalyst con centration produce about 50% less trans than normal

� High pressures and catalyst concentration are deter rents to commercial use� Work about 10 years ahead of its time

King, et. al. "Hydrogenation of Soybean Oil in Mixtures of Super C ritical Carbon Dioxide and Hydrogen," JAOCS, 78 107–113 (2001)

List, et. al. "Hydrogenation of Soybean Oil: Effect of Pressure o n Selectivity,"JAOCS 77 311–314 (2000)

� Trans suppression up to 80% — slow reaction rates at low t emperatures and high pressures (i.e. 120ºC, 250–500 lbs.)

� Studies strongly suggest that a window exists where pressure and temperature can be used to make a selective reaction rather tha n non-selective

Warner, et. al. "Electrochemical Hydrogenation of Soybean Oil," JAOCS 77 (2000)

� Shows promise in laboratory studies

Trans Acid Reduction During HydrogenationTrans Acid Reduction During Hydrogenation

Trans and Saturate Formation:Effect of Catalyst

Trans and Saturate Formation:Effect of Catalyst

Ariaansz and Okonek, World Conference Proceedings (1998)Ariaansz and Okonek, World Conference Proceedings (1998)

5500

1010

2020

3030

4040

5050

1010 1515 2020 2525

% Saturates at 70 IV% Saturates at 70 IV

% T

ran

s Is

omer

s at

70

IV%

Tra

ns

Isom

ers

at 7

0 IV

3030

RuRu

PtPt

PdPd

Pt (Mod)Pt (Mod)

NiNi

Commercial Solutions for Trans ReductionCommercial Solutions for Trans Reduction

Company Solutions

A Naturally stable oils, lauric / palm fats, blends, interesterified (chemical / enzymatic)

B Low trans / low saturate baking shortenings, cocoa butter replacers, palm- / palm-kernel based

C Low trans, reduced saturate baking shortenings, low linolenic soybean, canola oil

D Zero trans liquid oils, low trans / low saturate baking shortenings

E Palm-based baking shortenings, palm-based frying fats, low trans coating fats

F Palm-based structural fats for spreads / baking shortenings, fractionation / interesterification

Company Solutions

A Naturally stable oils, lauric / palm fats, blends, interesterified (chemical / enzymatic)

B Low trans / low saturate baking shortenings, cocoa butter replacers, palm- / palm-kernel based

C Low trans, reduced saturate baking shortenings, low linolenic soybean, canola oil

D Zero trans liquid oils, low trans / low saturate baking shortenings

E Palm-based baking shortenings, palm-based frying fats, low trans coating fats

F Palm-based structural fats for spreads / baking shortenings, fractionation / interesterification

THANK YOU! THANK YOU!